minerals

Article
A Case Study of Enhanced Sulfidization Flotation of
Lead Oxide Ore: Influence of Depressants
Haiyun Xie, Rui Sun , Jizong Wu, Dongxia Feng * and Likun Gao
Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, China;
xie-haiyun@163.com (H.X.); kmust_sun@163.com (R.S.); wjz0799@gmail.com (J.W.); likun_gao@126.com (L.G.)
* Correspondence: dongxia.feng@uqconnect.edu.au; Tel.: +86-0871-65153408




Received: 8 November 2019; Accepted: 19 January 2020; Published: 22 January 2020


Abstract: The refractory lead oxide ore has become an important source of lead metal with the
continuous depletion of lead sulfide minerals. Lead oxide ore is of poor floatability and there are few
cases to concentrate it successfully. In this study, the sulfidization-xanthate flotation method is applied
for the beneficiation of lead oxide ore in Yunnan Province (China) with sodium hexametaphosphate
and carboxymethyl cellulose as depressant. Chemical analysis and phase analysis was performed
to explore the physicochemical property of raw ore, which provides a research basis for process
design and operational control. The main influencing factors during the process, including grinding
fineness, reagent types, and dosage, etc., have been studied through flotation tests. Zeta potential
measurements and Fourier transfer-infrared spectrometry (FTIR) analysis were conducted to reveal
the function mechanism of the reagents. Based on the determined experimental conditions, open
circuit tests and closed circuit tests with one stage rougher, three-stage scavenger, and two-stage
cleaner flotation, were carried out with the run-of-mine ore with a lead grade of 4.57%. Through close
circuit bench test, the lead concentrate with a lead grade of 64.08% and recovery of 92.30% was
obtained. This study is of special value, as it provides referencing significance for economically
exploiting lead oxide ore.

Keywords: lead oxide ore; sulfidization flotation; depressants

1. Introduction
Lead is an important industry material, which is widely used in electrical, mechanical, chemical,
metallurgy, pharmaceutical, military, and other fields [1]. Naturally, lead resources are divided into
lead oxide ore and lead sulfide ore. Lead sulfide ore, especially galena, is the main raw material
for lead production, because of its good natural floatability [2–4]. However, with the increasing
consumption of lead metal, the resources of lead sulfide cannot meet the continuing high demand,
so the exploitation and utilization of lead oxide ore is imperative. The lead oxide ore, mainly including
cerussite (PbCO3 ), lead alum (PbSO4 ), is derived from lead sulfide ore after being interacted with
oxygen, carbon dioxide, underground water, and bioorganic matter, etc. The gangue minerals in
lead oxide are mainly chlorite, serpentine, calcite, quartz and feldspar, quartz, clay, etc. Thus, very
fine particles and a lot of slime are easily generated during crushing and grinding, which greatly
interfere with the flotation performance of lead oxide ore [5,6]. In this study, the ore sample from
Yunnan Province are cerussite and galena with non-metallic minerals (mainly chlorite and serpentine).
The degree of oxidation is quite high, about 80.52%, and the gangue minerals are easily sliming during
crushing and grinding. Therefore, the flotation process is deteriorated by a large number of fine
particles and the separation process is difficult.
At present, lead oxide ore is mainly enriched by the sulfuration flotation method, while other
technologies, such as leaching and roasting, are not widely used because of their high cost [7].

Minerals 2020, 10, 95; doi:10.3390/min10020095 www.mdpi.com/journal/minerals

Minerals 2020, 10, 95 2 of 13

In the case of the lead-oxide ores, sulfurization-xanthates flotation methods are usually applied.
After being conditioned by sodium sulfide as sulfurizing reagent, xanthate, and other reagents
were added subsequently. The sulfurization-xanthates flotation method has outstanding merits.
After being sulfurized by sodium sulphide, the surface of lead oxide ore is modified and the surface
electronegativity and hydrophobicity are increased, which is similar to sulfide minerals. Thus the
xanthates collector is more easily adsorbed on the mineral surface and forms a lead-xanthates complex,
which can significantly improve the floatability of the lead oxide ore without pre-desliming treatment [8].
The sulfidization-xanthate flotation method was successfully employed in many cases, but for different
ore deposit, specific research on the equipment operation, process design, and reagents regime are
required to obtain a satisfactory result.
Apart from a collector and activator, a depressant plays an important role in controlling the gangue
entrainment in fine particle flotation. Typically, sodium silicate and sodium hexametaphosphate
are added as depressant in sulfidization-xanthates flotation of oxide ore minerals [9]. In this case,
carboxymethyl cellulose (CMC) is tentatively added to help depress fine gangue minerals and improve
the flotation performance. CMC is one of important organic macromolecular depressants and it
most widely used to depress gangue minerals that contain calcium and magnesium in the flotation
process [10–12]. Its possible interaction mechanisms between polymers and the talc surface involve one
or more of chemical, electrostatic, hydrogen, and hydrophobic bonding contributions. The generally
recognized mechanism is that CMC can adsorb on the gangue mineral surfaces, and the adsorbed
hydroxyl groups can form hydration shell through hydrogen bonding, resulting more hydrophilic
surface and lower floatability [13–15].
In this work, exploratory research work was focus on the specific raw lead oxide ore with
the sulfidization-xanthate flotation method, in aspects of process design and reagents regimes.
Chemical analysis and phase analysis was performed to explore the physicochemical property of raw
ore, which provides the research basis for process design and operational control. Flotation tests were
conducted and results are to diagnose and determine the operation conditions and the flow sheet
design. Zeta potential and FTIR characterization were conducted to understand the sulfidization
mechanism of sodium sulfide on the lead oxide mineral surface. The depressing mechanism of CMC
was studied via zeta potential measurements. This study lays the research foundation for the efficient
separation and enrichment of lead oxide resources.

2. Materials and Methods

2.1. Mineralogical Analysis of Raw Ore

The raw ore is from Tengchong mine, Yunnan Province. Spectrum analysis (ICP-OES, German)
was applied to semi-quantitatively determine the element types and their content, as shown in
Table 1. Lead, calcium, silicon, magnesium, iron, and aluminum are the main elements in the raw
ore. Subsequently, atomic absorption spectrophotometer (4530F, China) was employed to quantify
the valuable elements and gangue components, as shown in Table 2. The results showed that the ore
has a lead grade of 4.57% and a quite low other metals content. According to the data of element
analysis, X-ray diffractometer (XRD, BTX-II, Guangyu Tech, Taipei, Taiwan) analysis was performed
to determine the mineralogical composition of the raw ore, as shown in Table 3. The results indicate
that the lead oxide ore is mainly sandstone type ore and metallic minerals are mainly cerussite, lead
alum and galena, and the gangue minerals are mainly chlorite and serpentine, followed by calcite,
quartz, and feldspar, etc., Pb phase analysis was carried out to further confirm the lead mineral type.
Lead oxide and lead sulfide contents of the ore were assayed by the titration method and content of
insoluble lead was measured by Atomic Absorption Spectrometry (WFX-120, Ruida Tech, Beijing,
China). The weight fraction of lead chemical compounds (wB/%) and lead weight fraction in raw ore
(wPb/%) were presented in Table 4. It indicates a high degree of oxidation with approximately 80.52%
of lead minerals that are distributed in carbonates and sulfate.
Minerals 2020, 10, 95 3 of 13

Minerals 2020, 10, 95 Table 1. Spectrum Analysis results of raw ore/%. 3 of 13

Ba As Al STable 1.Mg
SpectrumMn
Analysis Si
results of Zn Fe
raw ore/%. Ca Cu Pb
0.12 Ba <0.1As >1Al 0.30S >1
Mg <0.1
Mn >4
Si <0.1
Zn Fe 1 Ca>5 Cu<0.1 Pb >1
0.12 <0.1 >1 0.30 >1 <0.1 >4 <0.1 1 >5 <0.1 >1
Table 2. Multi-element analysis results of ore/%.
Table 2. Multi-element analysis results of ore/%.
Pb Zn S Cu Fe SiO2 CaO MgO Al2 O3
4.57Pb Zn
0.01 S
0.33 Cu
0.01 Fe
1.21 SiO 2
34.56 CaO
18.24 MgO
9.31 Al2O 3
7.65
4.57 0.01 0.33 0.01 1.21 34.56 18.24 9.31 7.65
Table 3. Mineralogical composition of raw ore/%.
Table 3. Mineralogical composition of raw ore/%.
Cerussite Lead Alum Galena Quartz Chlorite Serpentine Calcite Feldspar Others Total
Cerussite Lead Alum Galena Quartz Chlorite Serpentine Calcite Feldspar Others Total
3.88
3.88 0.93
0.93 0.98
0.98 10.56
10.56 29.14
29.14 28.67
28.67 12.59
12.59 8.22
8.22 5.03
5.03 100100

Table4.4.Analysis
Table Analysis results of
of lead
leadphase.
phase.

Lead
Lead Phase
Phase Carbonate
Carbonate Sulfate
Sulfate Sulfide
Sulfide others
others Total
Total
wB/% 65.76 15.76 16.61 1.87 100.00
wB/% 65.76 15.76 16.61 1.87 100.00
wPb/%
wPb/% 3.01
3.01 0.67
0.67 0.85
0.85 0.04
0.04 4.57
4.57
Pb
Pb Distribution/%
Distribution/% 65.86
65.86 14.66
14.66 18.60
18.60 0.88
0.88 100.00
100.00

2.2. Flotation Tests

2.2. Flotation Tests
Rougher flotation tests were carried out by one stage rougher and three stage scavengings to
Rougher flotation tests were carried out by one stage rougher and three stage scavengings to determine
determine the optimum experimental conditions, including the optimal particle size fraction for
the optimum experimental conditions, including the optimal particle size fraction for flotation and the
flotation and the optimum reagents’ dosage (Figure 1). The raw ore (300 g) was first ground with a
optimum
cone ball reagents’ dosage (Figure
mill (XMQ-240 1). The raw
× 90). Flotation testsore (300conducted
were g) was firstinground
a singlewith a cone
flotation ball
cell millof(XMQ-240
(XFD 0.75 L
× 90). Flotation tests were conducted in a single flotation cell (XFD of
and 1 L) with adding sodium sulfide (Na2S) as sulfurizing reagent, carboxymethyl cellulose 0.75 L and 1 L) with adding
(CMC),
sodium sulfide (Na S)
sodium hexametaphosphate
2 as sulfurizing reagent, carboxymethyl cellulose (CMC), sodium hexametaphosphate
(NaPO3)6, and sodium silicate (Na2SiO3) as depressants, butyl xanthate
(NaPO )6 , and
and 3butyl sodium silicate
ammonium (Na2as
aerofloat SiO 3 ) as depressants,
collectors, and pine butyl
oil as xanthate andfirst
frother. The butyl
stepammonium aerofloat
is to determine the as
collectors,
optimum and pine
size oil as frother.
fraction The first
for flotation, i.e.,step is togrinding
proper determine the optimum
fineness. Optimal sizereagents
fraction dosages
for flotation,
werei.e.,
proper grinding
determined byfineness.
flotation Optimal
tests afterreagents
confirmingdosages were determined
the optimum by flotation
size fraction tests after
of the flotation feed.confirming
Finally,
thethe
optimum size fraction
open circuit flotationof the
test flotation
and closed feed.circuit
Finally, the open
flotation circuit
test was flotation
carried out test to
and closed circuit
examine the
feasibility
flotation test of
was thecarried
process.
outThe pH Value
to examine theduring the flotation
feasibility was monitored
of the process. The pH Value by a precise
during pH meter
the flotation
was(FE20, MettlerbyToledo,
monitored Zurich,
a precise Switzerland).
pH meter (FE20, Mettler Toledo, Zurich, Switzerland).

Crude ore
Time unit：mi n

Change of grinding fineness

Reagents
Roughing

3
Reagents
Scavenging Ⅰ

3
Reagents
Scavenging Ⅱ

3
Reagents
Scavenging Ⅲ

Pb ro ug h concentrate Tailing

Figure 1.1.Flow
Figure Flowchart
chartof
oftests
teststo
to determine the grinding
determine the grindingfineness
finenessand
andreagents’
reagents’ dosage.
dosage.
Minerals 2020, 10, 95 4 of 13
Minerals 2020, 10, 95 4 of 13

To examine
To examinethe therheological
rheologicaleffect
effect
of of serpentine
serpentine on the
on the flotation
flotation pulp,pulp, rheometer
rheometer (Anton(Anton Paar,
Paar, MCR
MCR 301, Antongpa, Graz, Austria) was used to detect the rheological property
301, Antongpa, Graz, Austria) was used to detect the rheological property of 35% (mass concentration) of 35% (mass
concentration)
pulp pulp ofwas
of Shear stress Shear stress was
measured measured
within shear within
rate fromshear
50rate from
to 300 50, as
s−1 to 300
showns−1, as
in shown
Figure in2.
Figure 2. The rheological curves show that the pulp is Newtonian fluid and there is
The rheological curves show that the pulp is Newtonian fluid and there is no big difference for theno big difference
for the
three three
kinds kinds of It
of samples. samples. It clearly
clearly tells that thetells that theinserpentine
serpentine this specificinore
this
hasspecific ore has little
little interference for
interference for the pulp viscosity or other rheological
the pulp viscosity or other rheological properties. properties.

0.3

Pure cerussite
Tailings
Feed minerals
Shear stress(Pa)

0.2

0.1

0.0
0 50 100 150
-1
Shear rate(s )

Figure
Figure 2. Rheological curve
2. Rheological curve of
of pure
pure cerussite
cerussite (dots), flotation feed
(dots), flotation feed (square)
(square) minerals
minerals and
and tailings
tailings
(triangle)
(triangle) with
with mass
mass concentration
concentration of
of 35%.
35%.
2.3. Zeta Potentials Measurements
2.3. Zeta Potentials Measurements
Zeta potential measurement was conducted by ZetaPlus potential analysis instrument (Brookhaven,
Zeta potential measurement was conducted by ZetaPlus potential analysis instrument
NY, USA). The mineral samples were ground in agate mortar until the particle size was less than 2 µm.
(Brookhaven, NY, USA). The mineral samples were ground in agate mortar until the particle size
20 mg of the mineral samples were conditioned of 0.04% concentration (mass fraction) in a beaker
was less than 2 μm. 20 mg of the mineral samples were conditioned of 0.04% concentration (mass
for a desired duration and then added with desired concentrations of the reagents. The pH of the
fraction) in a beaker for a desired duration and then added with desired concentrations of the
resulting suspension was adjusted by adding 0.1 mol/L sulfuric acid and 0.1 mol/L sodium hydroxide
reagents. The pH of the resulting suspension was adjusted by adding 0.1 mol/L sulfuric acid and 0.1
solutions accordingly. The suspension samples were stirred with a magnetic stirrer for 5 min., and let
mol/L sodium hydroxide solutions accordingly. The suspension samples were stirred with a
it sit for 5 min. Afterwards, the suspension was injected into the electrode container for measurement.
magnetic stirrer for 5 min., and let it sit for 5 min. Afterwards, the suspension was injected into the
Each measurement was repeated three times and an average of the results was taken as the final result.
electrode container for measurement. Each measurement was repeated three times and an average
of the
2.4. results
FTIR was taken as the final result.
Analysis
Fourier
2.4. FTIR Transform Infrared Spectrometer (IRAffinity-1, Yisai Tech, Shanghai, China) was employed
Analysis
for characterizing the surface chemical properties of the pure galena, pure cerussite, and mineral
Fourier
particles afterTransform Infrared
sulfidization process.Spectrometer
According to (IRAffinity-1, Yisai
the literature, the Tech,
Pb-S Shanghai,
absorption China)
peaks appear was
at
employed for characterizing
−1 the surface chemical properties of the pure galena, pure cerussite,
wavenumber of 1643.3 cm [16], and the characteristic absorption peak for cerussite is approximately and
mineral
1718 cm−1particles
and 1396after sulfidization
cm−1 [17]. process. According to the literature, the Pb-S absorption peaks
appear at wavenumber of 1643.3 cm−1 [16], and the characteristic absorption peak for cerussite is
3. Results and Discussion
approximately 1718 cm−1 and 1396 cm−1 [17].

3.1. Effect ofand

3. Results Grinding Fineness
Discussion
Grinding fineness is an important factor affecting the flotation efficiency of lead oxide ore.
3.1. Effect
The of Grinding
liberation degreeFineness
would be low if particles were not ground fine enough, and the flotation
performance
Grinding would be negatively
fineness affected,
is an important bothaffecting
factor in recovery
therate and concentrate
flotation efficiency grade.
of leadHowever,
oxide ore.ifThe
the
particles
liberationwere ground
degree too be
would fine,low
apart
if from an increase
particles were notof energy
groundconsumption,
fine enough,there and would occurs
the flotation
serious sliming
performance which
would also exertsaffected,
be negatively negativebothimpact on flotation
in recovery efficiency.
rate and Therefore,
concentrate grade. appropriate
However, if
grinding fineness
the particles wereshould
ground be too
guaranteed in order
fine, apart from toanachieve satisfactory
increase of energyresults.
consumption, there would
occursFlotation
serioustests process
sliming werealso
which carried outnegative
exerts accordingimpact
to the on
flow sheet (Figure
flotation 1). The
efficiency. slurry
Therefore,
concentration in grinding
appropriate grinding wasshould
fineness 65% and be the rougher in
guaranteed dosage
orderoftoeach reagent
achieve was 2000
satisfactory g/t of sodium
results.
Minerals 2020, 10, 95 5 of 13

Minerals 2020, 10, 95 5 of 13

Flotation tests process were carried out according to the flow sheet (Figure 1). The slurry
concentration in grinding was 65% and the rougher dosage of each reagent was 2000 g/t of sodium
sulphide, 100
sulphide, 100 g/t
g/tof
ofbutyl
butylxanthate,
xanthate,6060g/t
g/tofofbutyl
butyl ammonium
ammonium aerofloat,
aerofloat, and
and 80 80
g/t g/t of pine
of pine oil, oil,
withwiththe
the dosage
dosage of reagents
of reagents for each
for each scavenging
scavenging waswas halved
halved in order.
in order.
Referring totothe
Referring thegrinding
grinding tests
tests results
results that that are shown
are shown in Tablein5,Table 5, with
with the theofincrease
increase of the
the proportion
proportion of particles of −0.074 mm, the lead grade and recovery rate increased and
of particles of −0.074 mm, the lead grade and recovery rate increased and then decreased. When the then decreased.
When the percentage
percentage of −0.074 mm of −0.074 mmaccounted
particles particles accounted
for 80.00%,forthe
80.00%, the lead
lead grade wasgrade
14.01% wasand14.01%
recoveryand
rate was 92.49%. Therefore, it is determined that the optimum grinding fineness is the proportionthe
recovery rate was 92.49%. Therefore, it is determined that the optimum grinding fineness is of
proportion
−0.074 mm,of −0.074 mm,
accounting foraccounting
80.00%. for 80.00%.

Table 5. Results
Table 5. Results of
of grinding
grinding fineness
fineness tests.
tests.

−0.074
−0.074 Proportion/% Yield/%
Proportion/% Yield/% PbPb
Grade/%
Grade/% Pb Recovery/%
Pb Recovery/%
60.00 19.53 20.44 86.93
60.00 19.53 20.44 86.93
70.00 70.00 27.77
27.77 14.09
14.09 89.33 89.33
80.00 80.00 28.85
28.85 14.01
14.01 92.49 92.49
90.00 90.00 32.16
32.16 13.50
13.50 91.98 91.98

3.2. Effect of Sulfidization Reagent

3.2.1. Determination of Sodium Sulfide Dosage

The aim of suphurization is to change the physical and chemical properties of oxidized mineral
surface and
andmodify
modify thethe
ionion
composition
composition of pulp with adding
of pulp with addingsulphidiser, so as to enhance
sulphidiser, so as tothe floatability
enhance the
of minerals of
floatability and achieveand
minerals the achieve
separationthe and enrichment
separation of oxidized of
and enrichment minerals.
oxidizedThe right amount
minerals. The rightof
sodium
amount sulfide
of sodiumshows good
sulfide activation
shows effect for lead
good activation effectoxide ore oxide
for lead in sulfidization-xanthate flotation.
ore in sulfidization-xanthate
In solution,
flotation. Insodium
solution,sulfide
sodiumhydrolyses
sulfide and then releases
hydrolyses and thenS2− and HS− S
releases ions intoHS
2− and solution. Sulphur
− ions into ions
solution.
pass into ions
Sulphur the crystal
pass intolattice
theofcrystal
the oxidised
lattice minerals from the
of the oxidised surface,from
minerals formingthe an insoluble
surface, subside
forming an
sulfide surface and enhancing the hydrophobicity of the mineral surface. The S2− can adsorb on
insoluble subside sulfide surface and enhancing the hydrophobicity of the mineral surface. The S2−
surfaces
can adsorb of lead oxide minerals,
on surfaces of lead increasing its hydrophobicity
oxide minerals, increasing its[18]. However, the[18].
hydrophobicity dosage of sodium
However, the
sulfide
dosage must be strictly
of sodium controlled,
sulfide must be as higher
strictlydosage wouldasplay
controlled, a roledosage
higher of depressant
would andplayprevent
a roletheof
adsorption of collector on mineral surface [19].
depressant and prevent the adsorption of collector on mineral surface [19].
The grinding
grindingfineness
finenesswas was −0.074 mm,
−0.074 mm,accounting
accounting for 80.00%. The dosage
for 80.00%. range range
The dosage of sodium sulfide
of sodium
in the Pb
sulfide inrougher flotationflotation
the Pb rougher was 500–3000 g/t. Other
was 500–3000 g/t.conditions are 100 g/t
Other conditions areof100
butyl
g/t xanthate, 60 g/t of
of butyl xanthate,
butyl
60 g/tammonium aerofloat, 80
of butyl ammonium g/t of pine
aerofloat, 80oil,
g/tand the dosage
of pine oil, andforthe
each scavenging
dosage for eachwasscavenging
halved in order.
was
As shown
halved in in Figure
order. As3,shown
2000 g/tinisFigure
the best
3, dosage
2000 g/tofissodium
the best sulfide
dosagewith
of the lead grade
sodium sulfidewas 16.21%
with and
the lead
the
graderecovery was 98.38%.
was 16.21% and the recovery was 98.38%.

20 100
Pb Grade
Pb Recovery

95
Pb Recovery/%
Pb Grade/%

15

90

10 85
500 1000 1500 2000 2500 3000

Sodium sulfide /（g/t）

Figure
Figure 3. The influence
3. The influence of
of Na
Na22SS dosage
dosage on
on Pb
Pb rougher
rougher flotation.
flotation.
Minerals 2020, 10, 95 6 of 13
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3.2.2.
3.2.2. Characterization
3.2.2. Characterization of
Characterization of Sulfidization
of Sulfidization Process
Sulfidization Process
Process
FTIR
FTIR analysis
FTIR was
analysis was
analysis conducted
was conducted with
conducted with the
withthe sulfuring
thesulfuring cerussite.
sulfuringcerussite. The
cerussite.The results
Theresults that
resultsthat are
thatare shown
showninin
areshown Figure
inFigure
Figure4
4clearly
4 clearly indicate
clearlyindicate
indicatethethe formation
formationofof
theformation sulfide
ofsulfide
sulfideon on cerussite
oncerussite surface.
cerussitesurface. New
surface. New absorption
absorption peak
New absorption peak appears at
peak appears
appears at
at
1643.3
1643.3 cm
1643.3 cm−1when
cm
−1
−1
whencompared
when comparedwith
compared withthe
with thepure
the puregalena
pure galena and
galena and cerussite
and cerussite minerals,
cerussite minerals, which
minerals, which is
which is the
is the characteristic
the characteristic
characteristic
peak
peak of Pb–S. What is more, the peak of cerussite shifts from 1718.16 cm to 1722.57 cm−1,,, and
peak of
of Pb–S.
Pb–S. What
What is
is more,
more, the
the peak
peak of
of cerussite
cerussite shifts
shifts from
from 1718.16
1718.16 cm
cm −1 to
−1
−1 to 1722.57
1722.57 cm
cm −1 and the
−1 the
and the
intensity
intensity and peak area decreases distinctly, which indicates a reasonable sufidization reaction on
intensity and
and peak
peak area
area decreases
decreases distinctly,
distinctly, which
which indicates
indicates a
a reasonable
reasonable sufidization
sufidization reaction
reaction on
on
cerussite
cerussite surface.
cerussite surface.
surface.

11
Transmittance(%)

1643.3
1643.3

22 1722.57
1722.57
1643.3
1643.3

1396.36
1396.36

33
1718.16
1718.16

1396.18
1396.18

4000
4000 3500
3500 3000
3000 2500
2500 2000
2000 1500
1500 1000
1000 500
500
Wavenumber(cm-1
Wavenumber(cm -1
))

Figure
Figure 4.
4. Infrared
Infrared spectra
spectra of
of different
different samples:
samples: (1)
(1) Pure
Pure galena
galena mineral;
mineral; (2)
(2) Sulfidized
Sulfidized Cerussite;
Cerussite; (3)
Cerussite; (3)
Pure
Pure cerussite
cerussite mineral.
mineral.

The zeta
The zetapotential
zeta potentialofof
potential cerussite
of cerussite
cerussite solution andand
solution
solution cerussite
and withwith
cerussite
cerussite appropriate
with amount
appropriate
appropriate of sodium
amount
amount of sulfide
of sodium
sodium
(2000
sulfideg/t)
sulfide wasg/t)
(2000
(2000 measured
g/t) was from pH
was measured
measured = 4pH
from
from to 11.
pH == 44As
to shown
to 11.
11. As in Figure
As shown
shown in 5, the cerussite
in Figure
Figure 5,
5, the surface
the cerussite
cerussite was more
surface
surface was
was
negatively
more charged
more negatively
negatively at eachat
charged
charged atcondition
each after adding
each condition
condition after sodiumsodium
after adding
adding sulfide.sulfide.
sodium The pHThe
sulfide. isoelectric
The pH point (IEP)
pH isoelectric
isoelectric of
point
point
cerussite
(IEP)
(IEP) of decreased
of cerussite
cerussite from 5.85
decreased
decreased to 4.82.
from
from 5.85It
5.85 toindicates
to 4.82.
4.82. It the formation
It indicates
indicates the of metalof
the formation
formation sulfide
of metalfilm
metal [20].film
sulfide
sulfide film [20].
[20].

20
20
Cerussite
Cerussite
10
10 Cerussite+Na
Cerussite+Na22SS

00
Zeta potential,mV

-10
-10

-20
-20

-30
-30

-40
-40

-50
-50
44 55 66 77 88 99 10
10 11
11

pH
pH

Figure
Figure 5.
Figure 5. Zeta
5. Zetapotential
Zeta potentialof
potential ofcerussite
of cerussiteat
cerussite atdifferent
at different pH
different pH in
pH in deionized
in deionized water
deionized water and
water and sodium
and sodium sulfide
sodium sulfide solution.
sulfide solution.
solution.

3.3.
3.3. Effect of
3.3. Effect
Effect of Depressing
of Depressing Reagents
Depressing Reagents
Reagents

3.3.1.
3.3.1. Sodium Silicate
3.3.1. Sodium
Sodium Silicate and
Silicate and Sodium
and Sodium Hexametaphosphate
Sodium Hexametaphosphate
Hexametaphosphate
The
The high
The highcontent
high contentalkaline
content alkaline
alkalinegangue
gangue
ganguein Yunnan
in
in Yunnan
Yunnan leadlead
oxide
lead ore shows
oxide
oxide ore serious
ore shows
shows sliming.
serious
serious SodiumSodium
sliming.
sliming. silicate
Sodium
can hydrolyze to silicictoacid. H2 acid.
SiO 2−
silicate
silicate can
can hydrolyze
hydrolyze to silicic
silicic 3 and
acid. H
H22SiO
SiOSiO andcan
33 3
and SiOeasily
SiO canadsorb
2− can
332− easilyon
easily the surface
adsorb
adsorb on theof
on the gangue
surface
surface ofminerals
of gangue
gangue
and enhance
minerals
minerals and its hydrophilicity,
and enhance
enhance its thus leading
its hydrophilicity,
hydrophilicity, thus to the
thus leading stable
leading to suspension
to the
the stable of gangue
stable suspension
suspension of minerals
of gangue in solution.
gangue minerals
minerals in
in
However,
solution. when
solution. However, the
However, whendosage
when the of sodium
the dosage
dosage of silicate
of sodium increases,
sodium silicate silicic acid
silicate increases, tends
increases, silicic to form
silicic acid micelle
acid tends
tends to and
to form further
form micelle
micelle
and
and further
further polymerize
polymerize and
and finally
finally precipitate
precipitate into
into the
the solution.
solution. Hence,
Hence, the
the effective
effective components
components
Minerals 2020, 10, 95 7 of 13

Minerals 2020, 10, 95 7 of 13

polymerize and finally precipitate into the solution. Hence, the effective components H2 SiO3 and
SiO 2−
3 3 decrease,
H2SiO and SiO3which weakens
2− decrease, the inhibition
which weakens the ability of sodium
inhibition silicate
ability on gangue
of sodium minerals,
silicate which
on gangue
results
minerals,in awhich
decline in theingrade
results and recovery
a decline in the grade of lead
and concentrate
recovery of accordingly
lead concentrate[21]. accordingly [21].
Sodium
Sodium hexametaphosphate
hexametaphosphate can react with the calcium and magnesium ions in the solution solution to to
form a hydrophilic and stable complex, which has a good inhibitory
form a hydrophilic and stable complex, which has a good inhibitory effect on the minerals effect on the minerals containing
calcium
containing andcalcium
magnesium and [22]. The adsorption
magnesium [22]. The of sodium
adsorption hexametaphosphate on the mineral surface
of sodium hexametaphosphate on the
can also increase
mineral surface can the also
electronegativity of the surface and
increase the electronegativity ofseparate
the surfacethe and
mineral fromthe
separate other negatively
mineral from
charged mineralscharged
other negatively under the electrostatic
minerals under the repulsion forces.
electrostatic Therefore,
repulsion sodium
forces. silicate
Therefore, and sodium
sodium silicate
hexametaphosphate
and sodium hexametaphosphate were used aswere depressant
used as(for calcite, dolomite,
depressant silicate,
(for calcite, etc.) could
dolomite, enhance
silicate, the
etc.) could
slurry dispersion [23]. While its dosage exceeds a modest amount, the
enhance the slurry dispersion [23]. While its dosage exceeds a modest amount, the complex that wascomplex that was formed by the
reaction
formed by willthenotreaction
all remain willonnot
theallsurface
remain of calcite,
on the but also disperse
surface of calcite,inbutthe also
pulp.disperse
After itsinadsorption
the pulp.
onto
Aftertheitslead oxide surfaces,
adsorption onto the it will
leadalsooxide cause inhibition,
surfaces, which
it will also results in a decrease
cause inhibition, in theresults
which grade andin a
recovery rate of lead concentrate.
decrease in the grade and recovery rate of lead concentrate.
The
The rougher
rougherstagestagedosages
dosagesofofsodiumsodium silicate
silicateandandsodium
sodium hexametaphosphate
hexametaphosphate are are g/t +g/t
100100 100 g/t,
+ 100
200 200+g/t
g/t, g/t 200 g/t,g/t,
+ 200 300300 + 300
g/t g/t + 300g/t,g/t,
400 400 + +400
g/tg/t 400g/t,
g/t,respectively.
respectively.The Theother
otherconditions
conditionsare are grinding
grinding
fineness−0.074
fineness −0.074mm mmaccounting
accountingfor for80.00%,
80.00%, 2000
2000g/tg/t
of sodium
of sodium sulphide,
sulphide,300 g/t
300ofg/tCMC, 100 g/t
of CMC, 100of butyl
g/t of
xanthate, 60 g/t of
butyl xanthate, 60butyl
g/t ofammonium
butyl ammonium aerofloat,aerofloat,
and 80 g/tand of pine
80 g/toil,ofthe dosage
pine for each
oil, the dosagescavenging
for each
was halved in
scavenging order.
was As is
halved inshown
order. inAsFigure
is shown 6, the
inlead grade
Figure andlead
6, the recovery
graderateandincreased
recovery up ratetoincreased
a certain
point
up toand then started
a certain point andto decrease with the
then started increase of
to decrease the the
with combined
increase dosage
of theofcombined
sodium silicate
dosage andof
sodium
sodium hexametaphosphate. Therefore, the combined
silicate and sodium hexametaphosphate. reagentthe
Therefore, dosage + 300 g/t)
(300 g/treagent
combined is determined
dosage (300 g/t +
as
300the grade
g/t) (28.72%) and
is determined recovery
as the grade (95.51%)
(28.72%) of and lead reach the
recovery maximum.
(95.51%) of lead reach the maximum.

30 100
Pb Grade
Pb Recovery

95
Pb Recovery/%
Pb Grade/%

25

90

20 85
100+100 200+200 300+300 400+400

Sodium hexametaphosphate and Sodium silicate/（g/t）

Figure6.6.The
Figure Theinfluence
influenceof
ofNa
Na22SiO
SiO33 and
and (NaPO
(NaPO33))66 dosage
dosage on
on Pb
Pb rougher
rougher flotation.
flotation.

3.3.2. Carboxymethyl Cellulose (CMC)

3.3.2. Carboxymethyl Cellulose (CMC)
The flotation tests were conducted to determine the right dosage of CMC. The grinding fineness
The flotation tests were conducted to determine the right dosage of CMC. The grinding fineness
was −0.074 mm accounting for 80.00%, the rougher stage dosage range of CMC was from 100 g/t to
was −0.074 mm accounting for 80.00%, the rougher stage dosage range of CMC was from 100 g/t to
400 g/t. For other reagents, it was 2000 g/t of sodium sulphide, 100 g/t of butyl xanthate, 60 g/t of butyl
400 g/t. For other reagents, it was 2000 g/t of sodium sulphide, 100 g/t of butyl xanthate, 60 g/t of
ammonium aerofloat, 80 g/t of pine oil, the dosage for each scavenging was halved in order.
butyl ammonium aerofloat, 80 g/t of pine oil, the dosage for each scavenging was halved in order.
As is shown in Figure 7, the lead grade and recovery rate increased to a certain dosage and
As is shown in Figure 7, the lead grade and recovery rate increased to a certain dosage and then
then decreased with the increase of CMC dosage. An excessive amount of CMC can increase the
decreased with the increase of CMC dosage. An excessive amount of CMC can increase the
electronegativity of not only the gangue surfaces but also the cerussite surfaces, which reduces the
electronegativity of not only the gangue surfaces but also the cerussite surfaces, which reduces the
adsorption possibility of xanthate collector, resulting in a decrease of the recovery and grade of the
adsorption possibility of xanthate collector, resulting in a decrease of the recovery and grade of the
cerussite. Therefore, the optimum dosage of CMC was set with 300 g/t with Pb recovery rate of 93.75%
cerussite. Therefore, the optimum dosage of CMC was set with 300 g/t with Pb recovery rate of
and Pb grade of 31.34%.
93.75% and Pb grade of 31.34%.
Minerals 2020, 10,
Minerals 2020, 10, 95
95 88 of
of 13
13
Minerals 2020, 10, 95 8 of 13

32.0 100
32.0 100
Pb Grade
Pb Grade
Pb Recovery
31.5 Pb Recovery
31.5
95

Recovery/%
95

Grade/%

Recovery/%
Grade/%
31.0
31.0

PbPb

PbPb
90
30.5 90
30.5

30.0 85
30.0
0 100 200 300 400 50085
0 100 200 300 400 500
CMC/（g/t）
CMC/（g/t）

Figure 7. The influence of CMC dosage on Pb rougher flotation.

The influence
Figure 7. The influence of CMC dosage on Pb rougher flotation.

Function Mechanism of CMC

3.3.3. Function
3.3.3. Mechanism of CMC
As introduced
As introduced in in previous
previous section,
section, thethe depressing
depressing mechanism
mechanism of of CMC
CMC has has been
been mostly
mostly studied
studied
In our case, the lead oxide ore contains aalot ofofserpentine and chlorite. It may act as
in talc flotation. In our case, the lead oxide ore contains a lot of serpentine and chlorite. It may actact
in talc flotation. In our case, the lead oxide ore contains lot serpentine and chlorite. It may as
dispersant
as dispersant as well
as wellasasdepressant.
depressant. CMC
CMC isisa anegatively
negatively charged
charged polymer
polymer with
with carboxyl substituent
dispersant as well as depressant. CMC is a negatively charged polymer with carboxyl substituent
groups along
groups along thecellulose
cellulose chain. It can adsorb on gangue mineral surfaces and alter the surface
groups alongthe the cellulosechain.chain. It can
It canadsorb
adsorb on gangue
on ganguemineral surfaces
mineral and alter
surfaces andthe surface
alter charge,
the surface
charge,
thus thus preventing
preventing the the agglomeration
agglomeration of of fine-grained
fine-grained minerals minerals
and slime and slimeon
coating coating
mineral onsurfaces,
mineral
charge, thus preventing the agglomeration of fine-grained minerals and slime coating on mineral
surfaces,
hence hence resulting
resulting a good particle dispersion [24,25]. Zeta potential measurement was
surfaces, hence aresulting
good particlea good dispersion
particle [24,25]. Zeta[24,25].
dispersion potential measurement
Zeta was performed
potential measurement to
was
performed
verify the to verify the
dispersing dispersing mechanism.
mechanism.
performed to verify the dispersing mechanism.
Figure 88shows
Figure shows thezeta zeta potentials of serpentine within different conditions at different pH
Figure 8 showsthe the zeta potentials
potentials of serpentine
of serpentine within different
within conditions
different at different
conditions pH value.
at different pH
value.
The The square
square line shows
line shows the zeta the zeta potential of serpentine in deionized water. After adding CMC
value. The square line shows thepotential of serpentine
zeta potential in deionized
of serpentine water.water.
in deionized After After
adding CMCCMC
adding with
with concentration
concentration of 150 of 150 the
mg/L, mg/L, the surface
surface potential potential
decreased decreased dramatically.
dramatically. The IEP The
of IEP of serpentine
serpentine decreases
with concentration of 150 mg/L, the surface potential decreased dramatically. The IEP of serpentine
decreases
from from
9.80 from
to 9.80
5.1.9.80
The to 5.1. Thepotential
surface potential was further reduced within the solution of sodium
decreases tosurface was further
5.1. The surface potential wasreduced within the
further reduced solution
within of sodium
the solution silicate
of sodium
silicate
and and sodium
sodium hexametaphosphate
hexametaphosphate with with concentration
concentration of 150 of 150 mg/L.
mg/L. It wentIt to
went
a to a quite
quite low low value
value after
silicate and sodium hexametaphosphate with concentration of 150 mg/L. It went to a quite low value
after adding
adding CMC CMC
(150 (150 mg/L)
mg/L) as is as is shown
shown in in upside
upside down down triangle
triangle line. line. There
There shows shows
the the same
same trend trend
with
after adding CMC (150 mg/L) as is shown in upside down triangle line. There shows the same trend
with chlorite,
chlorite, as shownas shown
in Figurein Figure 9.
9. The9.more The more negative of surface charges, the stronger repulsion
with chlorite, as shown in Figure The negative of surface
more negative charges,
of surface the stronger
charges, repulsion
the stronger occurs,
repulsion
occurs,
thus thus preventing
preventing the the cohesion
cohesion between between
the ganguethe particles.
gangue particles.
In In addition,
addition, surface surface negative
negative electric
occurs, thus preventing the cohesion between the gangue particles. In addition, surface negative
electric can
energy energy can effectively
effectively prevent
prevent prevent its interaction
its interaction with anionwith anion collector
collector xanthate.
xanthate.xanthate.
electric energy can effectively its interaction with anion collector
80
80 Serpentine Serpentine+CMC:150mg/L
Serpentine Serpentine+CMC:150mg/L
60 Serpentine+Na2SiO3+(NaPO3)6:150mg/L
60 Serpentine+Na2SiO3+(NaPO3)6:150mg/L
Serpentine+Na2SiO3+(NaPO3)6+CMC:150mg/L
Serpentine+Na2SiO3+(NaPO3)6+CMC:150mg/L
40
potential/mV

40
Zetapotential/mV

20
20
0
0
Zeta

-20
-20
-40
-40
-60
-60 4 5 6 7 8 9 10 11
4 5 6 7 8 9 10 11
pH
pH

Figure 8. Zeta potential of serpentine at different pH.

pH.
Figure 8. Zeta potential of serpentine at different pH.
Minerals 2020,
Minerals 2020, 10,
10, 95
95 99 of
of 13
13
Minerals 2020, 10, 95 9 of 13
40
Chlorite
40
Chlorite+CMC:150mg/L
20 Chlorite
Chlorite+Na2SiO3+(NaPO3)6:150mg/L
Chlorite+CMC:150mg/L
20 Chlorite+Na
Chlorite+Na22SiO
SiO33+(NaPO
+(NaPO33))66+CMC:150mg/L
:150mg/L

potential/mV
0
Chlorite+Na2SiO3+(NaPO3)6+CMC:150mg/L

potential/mV
0
-20
-20

ZetaZeta
-40
-40
-60
-60
-80
4 5 6 7 8 9 10 11
-80
4 5 6 7 pH 8 9 10 11

pH
Figure 9. Zeta potential of chlorite at different pH.
Figure 9. Zeta potential of chlorite at different
Figure 9. different pH.
pH.
3.4. Effect of Collector Dosage
3.4. Effect of Collector Dosage
3.4. Effect of Collector Dosage
Xanthate and aerofloat collector molecules dissociate anionic hydrophobic sulfhydryl groups
Xanthate and aerofloat− collector molecules dissociate anionic hydrophobic sulfhydryl groups
[(RO)Xanthate
2CSS]− and and aerofloat
[(RO) 2PSS] collector
into water. molecules
After beingdissociate anionic
sulfurized hydrophobic
by sodium sulfhydryl
sulphide, groups
the surface of
[(RO)2 CSS]−− and [(RO)2 PSS]− − into water. After being sulfurized by sodium sulphide, the surface of
[(RO) CSS] and [(RO) PSS] into water. After being sulfurized by
lead oxide ore is similar to sulfide mineral PbS. Complexation chemical reaction takes place on
2 2 sodium sulphide, the surface of
lead oxide ore is similar to sulfide mineral PbS. Complexation chemical reaction takes place on mineral
lead oxide
mineral ore is between
surface similar to Pb sulfide
2+ andmineral PbS. Complexation
the hydrophobic sulfhydrylchemical reaction
groups. takescomplexes
Stable place on
surface between Pb2+ and the hydrophobic sulfhydryl groups. Stable complexes [(RO)2 CSS]2 Pb and
mineral
[(RO) 2CSS]surface
2Pb andbetween
[(RO)2PSS] Pb 2+ and the hydrophobic sulfhydryl groups. Stable
2Pb form on mineral surface through ionic bonding, thus complexes
enhancing
[(RO)2 PSS]2 Pb form on mineral surface through ionic bonding, thus enhancing the hydrophobicity of
[(RO)
the 2CSS]2Pb and [(RO)
hydrophobicity 2PSS]2Pb
of mineral form onThe
surfaces. mineral surface
chemical throughthat
reactions ionicmay bonding,
occur on thusthe
enhancing
mineral
mineral surfaces. The chemical reactions that may occur on the mineral surface are as following in
the hydrophobicity
surface are as following of mineral
in Equations surfaces.
(1) and The(2)chemical
[26,27]. reactions that may occur on the mineral
Equations (1) and (2) [26,27].
surface are as following in Equations (1) and (2) [26,27].
Pb2+ + 2(CH3 CH2 CH2 CH2 O)2 CSS− → 2[(CH3 CH2 CH2 CH2 O)2 CSS]2 Pb ↓ +2H + (1)
Pb2+Pb 2+
+2+
2(+ CH 3 CH
2(CH CH
2 CH CH
2 CH CH
2 O )
O) CSS
CSS
−−
→→ 2 [( CH
2[(CH 3 CH
CH 2 CH
CH CH
2 CH O)
2 O )
CSS]CSS ]
Pb Pb
↓ ↓
+2H+ + +
2H (1)
(1)
Pb + 2(CH33CH22CH22CH22O)2 22PSS− → 2[(CH3 CH22CH22CH22O)22PSS] 2 2 2
2 Pb ↓ +2H
+ (2)
2+Pb+2+2(+CH 2(CH 3 CH 2 CH2 CHO 2 O)2 PSS
−
− → 2[(CH3 CH2 CH2 CH2 O)2 PSS]2 Pb ↓ +2H
+
2H+ (2)
The Pbrougher stage 3 CH 2 CH2 CH
dosages 2 )2 PSS
range of butyl→ 2[( CH3 CH2and
xanthate CH2 CHbutyl2 O)ammonium
2 PSS]2 Pb ↓ + aerofloat (2)
were
The (40
between rougher
+ 40)–(100stage dosages
+ 70) Therange
g/t.range other of butyl xanthate
conditions and fineness
butyl ammonium aerofloat were
The rougher stage dosages of butyl xanthate areandgrinding
butyl ammonium −0.074
aerofloatmm accounting
were for
between (40
between2000
80.00%, (40 +g/t 40)–(100
of + 70) sulphide,
sodium g/t. The other300 conditions
g/t of CMC, are300
grinding
g/t of finenesssilicate,
sodium −0.074 mm 300 accounting
g/t of for
sodium
+ 40)–(100 + 70) g/t. The other conditions are grinding fineness −0.074 mm accounting for 80.00%, 2000 g/t
80.00%, 2000 g/t of sodium
hexametaphosphate and, sulphide, 300 g/t of CMC,for 300 g/t of sodium silicate, 300 ing/torder.
of sodium
of sodium sulphide, 300 g/t80of g/t
CMC,of pine oil,of
300 g/t the dosage
sodium each
silicate, 300scavenging
g/t of sodium was halved
hexametaphosphate Lead
and,
hexametaphosphate
recovery reached the and,
peak 80atg/t
the of 80
pineg/t oil,
of the dosage
butyl for each
xanthate and scavenging
60 g/t of butylwasammonium
halved in order. Lead
aerofloat,
80 g/t of pine oil, the dosage for each scavenging was halved in order. Lead recovery reached the peak at
recovery
while reached
theoflead the and
peakrecovery
at the 80 g/t of butyl xanthate and 60 g/t of100butyl ammonium aerofloat,
the 80 g/t butylgrade
xanthate and 60 g/t ofrate butyldecreased
ammonium at aaerofloat,
dosage about
while the leadg/tgrade
+ 70 g/t,
and as shown
recovery in
rate
while the
Figure 10. lead
As grade
from our and recovery of
perspective rate decreased
improving theatrecovery
a dosagerate,
about the 100
dosageg/t +of7080 g/t,
g/t as
+ 60shown
g/t in
was
decreased at a dosage about 100 g/t + 70 g/t, as shown in Figure 10. As from our perspective of improving
Figure 10.
adopted in Asthe from our perspective
following tests. of improving the recovery rate, the dosage of 80 g/t + 60 g/t was
the recovery rate, the dosage of 80 g/t + 60 g/t was adopted in the following tests.
adopted in the following tests.
34.0 100
34.0 Pb Grade 100
Pb
Pb Recovery
Grade
33.5 Pb Recovery
33.5 95
Pb Recovery/%
Pb Grade/%

95
Pb Recovery/%
Pb Grade/%

33.0
33.0
90
32.5 90
32.5

32.0 85
40+40 60+50 80+60 100+70
32.0 85
40+40 Butyl xanthate60+50 80+60
and Buty lammonium aerofloat /（g/t) 100+70
Butyl xanthate and Buty lammonium aerofloat /（g/t)
Figure 10. The
Figure 10. Theinfluence
influenceofof
butyl xanthate
butyl and and
xanthate butylbutyl
ammonium aerofloat
ammonium dosage dosage
aerofloat on Pb rougher
on Pb flotation.
rougher
Figure 10. The influence of butyl xanthate and butyl ammonium aerofloat dosage on Pb rougher
flotation.
flotation.
Minerals 2020, 10, 95 10 of 13
Minerals 2020, 10, 95 10 of 13

3.5. Open-Circuit
3.5. Open-Circuit Test
Test
The open
The opencircuit
circuittests
tests were
were performed
performed basedbased onabove
on the the above
resultsresults with optimum
with optimum grindinggrinding
fineness
fineness and reagents’ dosage for rougher flotation. The process includes one rougher,
and reagents’ dosage for rougher flotation. The process includes one rougher, two cleaner, twoand
cleaner,
three
and three scavenger stages, as shown is Figure 11. Table 6 gives the reagents dosage for
scavenger stages, as shown is Figure 11. Table 6 gives the reagents dosage for the three stages. the three
stages.
The The flotation
flotation experimentsexperiments were separately
were separately conducted conducted
with/withoutwith/without
CMC additionCMC addition the
for verifying for
verifying the depressing
depressing effect of CMC. effect of CMC.

Crude ore

（-0.074mm80%）

Rougher

Scavenging Ⅰ

Mid 3 Scavenging Ⅱ
Cleaner Ⅰ

Scavenging Ⅲ
Cleaner Ⅱ
Mid 2 Mid 4

Pb concentrate Mid 1 Mid 5 Tailing

Figure
Figure 11. Flow-sheets of
11. Flow-sheets of open
open circuit
circuit test.
test.

Table 6. Regent regime of open circuit test.

Table 6. Regent regime of open circuit test.
Dosage of Reagents with CMC (g/t)
Flowsheet Dosage of Reagents with CMC (g/t)
Na2 S CMC Na2 SiO3
(NaPO3 )6 C4 H6 OCSSNa (C4 H9 O)2 PSSNH4 Pine Oil
Flowsheet C4H6OCSS (C4H9O)2PSSN Pine
Rougher Na
2000 2 S CMC
300 Na 2
300SiO 3 (NaPO
300 3)6 80 60 80
Na H4 Oil
Scavenger I 1000 150 150 150 40 30 80
Rougher
Scavenger II 2000
500 300
100 300
100 100 300 20 80 20 60 80 80
Scavenger
Scavenger IIII 1000
250 150
50 150
50 50150 15 40 10 30 80 80
Cleaner II
Scavenger I -
500 -
100 100- - 100 40 20 30 20 80 80
Cleaner III
Scavenger II -
250 50- 50- - 50 30 15 20 10 80 80
Cleaner I - - - - 40 30 80
TableII7 displays-the open- circuits test
Cleaner - results with - one concentrate,
30 one tailing, and
20 five middlings.
80
The lead grade of concentrate can reach as high as 66.59% with lead recovery of 81.92%. The results
showTable
that the flotation performance
7 displays with CMC
the open circuits is muchwith
test results better than
one that without
concentrate, CMC.
one tailing, and five
middlings. The lead grade of concentrate can reach as high as 66.59% with lead recovery of 81.92%.
The results show that the flotation Table 7. Results of
performance open
with circuit
CMC is test/%.
much better than that without CMC.
Product CMC Pb Conc Midl 1 Midl 2 Midl 3 Midl 4 Midl 5 Tailing Crude Ore
Table 7. Results of open circuit test/%.
Yes 5.49 1.46 5.57 3.24 1.81 3.62 78.81 100
Yield/%
- 5.64 1.92 6.39 3.41 2.28 3.12 77.24 100
Crude
Product CMC Pb Conc Midl 1 Midl 2 Midl 3 Midl 4 Midl 5 Tailing
Yes 66.59 10.31 1.42 6.09 2.68 1.76 0.34 4.46
Ore
Pb grade/%
- 64.53 10.93 1.06 7.23 2.64 1.58 0.42 4.60
Yes 5.49 1.46 5.57 3.24 1.81 3.62 78.81 100
Yield/% Yes 81.92 3.37 1.77 4.42 1.09 1.43 6.00 100
Pb recovery% - 5.64 1.92 6.39 3.41 2.28 3.12 77.24 100
- 79.16 4.56 1.47 5.36 1.31 1.07 7.06 100
Yes 66.59 10.31 1.42 6.09 2.68 1.76 0.34 4.46
Pb grade/%
- 64.53 10.93 1.06 7.23 2.64 1.58 0.42 4.60
3.6. Closed-Circuit
Pb Yes Test 81.92 3.37 1.77 4.42 1.09 1.43 6.00 100
recovery% - 79.16 4.56 1.47 5.36 1.31 1.07 7.06 100
Closed-circuit test was carried out on the basis of the open-circuit test, the five middling products
were returned to roughing stage, as shown in Figure 12, to further verify the feasibility and rationality
 products were returned to roughing stage, as shown in Figure 12, to further verify the feasibility and
rationality of the whole process. The addition amount of the reagents was same with that in open
circuit test (Table 8).
When CMC is added throughout the process, the stable closed circuit test results are
Minerals 2020, 10, 95
demonstrated 11 of 13
in Table 8, with a satisfactory lead concentrate yield of 6.47%, lead grade of 64.08%,
and lead recovery rate of 92.30%, which is significantly improved than that without (grade 61.06%
and
of therecovery 90.16%).The
whole process. The results amount
addition indicateofthat
the CMC canwas
reagents significantly
same withenhance the depressing
that in open circuit test
procedure and facilitate the recovery of valuable lead minerals.
(Table 8).

Crude ore

（-0.074mm 80%）

Roughing

Cleaner Ⅰ Scavenging Ⅰ

Scavenging Ⅱ

Cleaner Ⅱ
Scavenging Ⅲ

Pb concentr ate Tailing

Figure 12. Flow-sheets

Figure 12. Flow-sheets of
of closed-circuit
closed-circuit tests.
tests.

Table 8. Results of closed-circuit test.

Table 8. Results of closed-circuit test.
Product CMC Pb Conc Tailing Crude Ore
Product CMC Pb Conc Tailing Crude Ore
Yes Yes 6.47
6.47 92.9392.93 100.00 100.00
Yield/%
Yield/% - 6.59 92.84 100.00
- 6.59 92.84 100.00
Yes Yes 64.08
64.08 0.380.38 4.87 4.87
Pb grade/%
Pb grade/% - 61.06 0.48 4.89
- 61.06 0.48 4.89
Yes Yes 92.30
92.30 7.267.26 100.00 100.00
Pb recovery%
Pb recovery% - 90.16 9.11 100.00
- 90.16 9.11 100.00

When CMC is added throughout the process, the stable closed circuit test results are demonstrated
4. Conclusions
in Table 8, with a satisfactory lead concentrate yield of 6.47%, lead grade of 64.08%, and lead recovery
This work was targeted to beneficiate the high-oxidation rate and refractory lead oxide ore in
rate of 92.30%, which is significantly improved than that without (grade 61.06% and recovery 90.16%).
Yunnan Province, China. The reagents regime and flow sheet were appropriate determined. A
The results indicate that CMC can significantly enhance the depressing procedure and facilitate the
decent result was obtained from close circuit test with lead concentrate yield of 6.47%, Pb grade of
recovery of valuable lead minerals.
64.08%, and Pb recovery rate of 92.30%. The addition of CMC can effectively depress the gangue
minerals
4. and significantly improve the mineral processing index of lead oxide ore. Adding CMC can
Conclusions
increase the grade of lead concentrate by 3.02% and lead recovery by 2.14% when compared with the
This work was targeted to beneficiate the high-oxidation rate and refractory lead oxide ore in
process without CMC. The sufidization mechanism of sodium sulfide was revealed with zeta
Yunnan Province, China. The reagents regime and flow sheet were appropriate determined. A decent
result was obtained from close circuit test with lead concentrate yield of 6.47%, Pb grade of 64.08%,
and Pb recovery rate of 92.30%. The addition of CMC can effectively depress the gangue minerals and
significantly improve the mineral processing index of lead oxide ore. Adding CMC can increase the
grade of lead concentrate by 3.02% and lead recovery by 2.14% when compared with the process without
CMC. The sufidization mechanism of sodium sulfide was revealed with zeta potential measurement
and FTIR analysis. The function mechanism of CMC was explored with the zeta potential method.
Minerals 2020, 10, 95 12 of 13

This work displays an integrated research approach for improving the recovering efficiency of the
lead oxide ore. However, there is possible room for improving the flotation performance and clarifying
the action mechanism of CMC on various gangue minerals. The reagents dosage determination test
should consider the interaction effect among the reagents. Additionally, the mechanism and application
of other macromolecular reagents in depressing gangue minerals could be further studied.

Author Contributions: Conceptualization, H.X. and L.G.; methodology, H.X.; software, J.W.; validation, R.S.
and J.W.; formal analysis, J.W.; investigation, R.S.; resources, L.G.; data curation, H.X.; writing—original draft
preparation, H.X.; writing—review and editing, D.F.; visualization, R.S.; supervision, D.F.; project administration,
H.X.; funding acquisition, H.X. and D.F. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Natural Science Foundation of China, grant number “51464030”
and “51804145”.
Acknowledgments: The authors gratefully acknowledge the academic scholarship of the Chinese Government
for the second author.
Conflicts of Interest: The authors declare no conflict of interest.

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